Method of combating weeds



Unired States Patent T O OF QM TIT NGNWIEE Harry Tilles, El Cerrito, and Joe Antognini, Mountain View, Calif., assignors to Stauifer Chemical Company,

acorporation of Delaware V No Drawing. Filed Oct. 13, 1958, Ser. No. 766,679

7 Claims. (Cl. 71 23) This invention relates to certain novel mercapto esters of disubstituted thiolcarbarnic acids as compositions of matter and as herbicides. The application is a continuation-in-pa'rt of application Serial No. 676,485, filed August 6, 1957, now abandoned. I h

More specifically, the invention relates to compounds of the general formula:

Code numbers have been assigned to each compound and are used throughout the balance of the application.

Patented June 20, 196i;

Example I (11-2264 )AA 500 cc. 4 neck flask waspj vided with stirrer, thermometer, condenserand g tube; a solution of 14.6 g.(0.20 mol) of diethyla'rn ne 20.2 g. (0.20 mol) of triethylaniine in 150 cc; gt pet leum ether, B.P. 60 C., was charged to'th'e' near; 4 d then 12 g. (0.20 mol) of carbonyl; sulfide wasbubb e into the amine solution with rapid stirring. It reCiu'iredQ minutes to complete the addition and the temperature s maintained at 23-325 CQWith cooling. The react if mixture was then cooled to 4 C. and 19.3 g. (0; 20'inol) of chlorodimethyl sulfide was added dropwise overutes, maintaining the temperature between .4'-7 C. 1th ice cooling. (In subsequent experiments, it was f i ld that it was uneeessary to cool the reaction mix M ing the addition, and the addition of the chlorodime thyl sulfide was usually begun between a temperature ra' e" of 15-25 C. and nocooling was employed.) 'Ih'ecool} ing was then removed and the temperature rose to 27 C. during the next 19 minutes; The mixture was then heated to reflux during the next 24 minutes and then cooled (o1 room temperature. The solid amine hydrochloride wa remoyed by filtration and the cake was washed with .2- cc. portions of petroleum ether. The combined filtrate was concentrated on the steam bath. The" residual liquid was then fractionallydistilled through an 18" Podbieliiial Heli-Grid Fractional Distillation'column. There was ob tained 16.5 g. (42.8% yield) f inethylmereap toniefthyl N,N-diethy1thi lcar'barnate, HP. (10 mm.) 140-1415 The novel compounds of thepresent inveiitionmay be made in accordance with the following nod-limiting ex- Found: N7.1'7%.

amples.

In the following examples, the carbonyl sulfide was add- 3 ed to the amine solution within a temperature range of 15-30 C.

Example II (R-2265).The general procedure of Example I was repeated except that 30.3 g. (0.30 mol) of di-n-propylamine, 25 g. (0.42 mol) of carbonyl sulfide, 30.3 g. (0.30 mol) of tn'ethylamine, 29.0 g. (0.30 mol) of chlorodimethyl sulfide and 200 cc. of petroleum ether, B.P. 30-60 C. solvent were employed. Instead of filtering the final reaction mixture, it was washed successively with 2-50 cc. portions of water, 250 cc. portions of dilute hydrochloric acid (5 cc. of concentrated hydrochloric acid made up to a volume of 50 cc. with water) and 2-50 cc. portions of water. The organic phase was then dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated on the steam bath. The residual liquid was then firactionally distilled. There was obtained 47.0 g. (71% yield) of methylmercaptomethyl N,N-din-propylthiolcarbamate, B.P. (4.5 mm.) 136.0137.5 C., 11 1.5157.

Analysis.-Calculated for C H NOS Found: N=6.20%.

Example III (R-2266).When the general procedure of Example II was repeated except that 26.1 g. (0.30 mol) of N-methyl-n-butylarnine, 30.3 g. (0.30 mol) of triethylamine, 25 g. (0.42 mol) of carbonyl sulfide, 29.0 g. (0.30 mol) of chlorodimethyl sulfide and 200 cc. of petroleum ether solvent were employed, there was obtained 45.1 g. (72.5% yield) of methylmercaptomethyl N-methyl-N- n-butylthiolcarbamate, B.P. (4.5 mm.) 136-137 C., r1 1.5212.

Analysis.-Calculated for C H NOS N=6.76%. Found: N=6.79%.

Example IV (R2267).--When the general procedure of Example II was repeated except that 30.3 g. (0.30 mol) of N-ethyl-n-butylamine, 30.3 g. (0.30 mol) of triethylamine, 25 g. (0.42 mol) of carbonyl sulfide, 29.0 g. (0.30 mol) of chlorodimethyl sulfide and 200 cc. of petroleum ether solvent were employed, there was obtained 42.6 g. (64.3% yield) of methylmercaptomethyl N-ethyl-N-n-butylthiolcarbamate, B.P. (4.5 mm.) 140 140.5 C., n 1.5155.

Analysis.-Calculated for C H NOS N=6.33%. Found: N=6.23%.

Example V (R-2296) .When the general procedure of Example H was repeated except that 38.1 g. (0.30 mol) of N-ethylcyclohexylamine, 30.3 g. (0.30 mol) of triethylamine, 25 g. (0.42 mol) of carbonyl sulfide, 29.0 g. (0.30 mol) of chlorodimethyl sulfide and 200 cc. of petroleum ether solvent were employed, there was obtained 29.6 g. (40.6% yield) of methylmercaptomethyl N-ethyl-N-cyclohexylthiolcarbamate, B.P. (4.5 mm.) 171.5-188 C., 1.5405.

Analysis.-Calculated for C H NOS N=5.66%. Found: N=5.53%.

Example Vl (R2323).-When the general procedure of Example II was repeated except that 29.1 g. (0.30 mol) of diallylamine, 30.3 g. (0.30 mol) of triethylarnine, 25

g. (0.42 mol) of carbonyl sulfide, 29.0 g. (0.30 mol) of chlorodimethyl sulfide and 200 cc. of petroleum ether solvent were employed, there was obtained 39.8 g. (61.0% yield) of methylmercaptomethyl N,N-diallylthiolcarbamate, B.P. (4.5 mm.) 139.0139.5% C., n 1.5405.

Analysis.-Calculated for C H NOS N=6.44%. Found: N=6.26%.

Example VII (R-2324).--When the general procedure of Example H was repeated except that 8.5 g. (0.10 mol) of N-allylethylamine, 10.1 g. (0.10 mol) of triethylamine, 10 g. (0.17 mol) of carbonyl sulfide, 9.7 g. (0.10 mol) of chlorodimethyl sulfide and 150 cc. of petroleum ether solvent were employed, there was obtained 10.0 g. (48.8%

4 yield) of methylmercaptomethyl N-allyl-N-ethylthiolcarbamate, B.P. (4.5 mm.) 131-132" C., n 1.5344.

Analysis.Calculated for C H NOS N=6.81%. Found: N=6.60%.

Example VIII (R-2326).-When the general procedure of Example II was repeated except that 9.9 g. (0.10 mol) of N-allyl-n-propylamine, 10.1 g. (0.10 mol) of triethylamine, 10 g. (0.10 mol) of carbonyl sulfide, 9.7 g. (0.10 mol) of chlorodimethyl sulfide and cc. of petroleum ether solvent were employed, there was obtained 8.5 g. (38.8% yield) of methylmercaptomethyl N-allyl-N-npropylthiolcarbamate, B.P. (4.5 mm.) 1405-1410 C., n 1.5280.

Analysis.Calculated for C H NOS N=6.38%. Found: N=6.28%.

Example IX (R-2328).-When the general procedure of Example 11 was repeated except that 9.9 g. (0.10 mol) of N-allyl-i-propylamine, 10.1 g. (0.10 mol) of triethylamine, 10 g. (0.17 mol) of carbonyl sulfide, 9.7 g. (0.10 mol) of chlorodimethyl sulfide and 150 cc. of petroleum ether solvent were employed, there was obtained 2.9 g,

(13.4% yield) of methylmercaptomethyl N-allyl-N-ipropylthiolcarbamate, B.P. (4.5 mm.) l35-136 C., u 1.5301.

Analysis-Calculated for C H NOS Found: N=6.60%.

Example X (R-2329).When the general procedure of Example II was repeated except that 11.3 g. (0.10 mol) of N-allyl-n-butylamine, 10.1 g. (0.10 mol) of triethylamine, 10 g. (0.17 mol) of carbonyl sulfide, 9.7 g. (0.10

mol) of chlorodimethyl sulfide and 150 cc. of petroleum i ether solvent were employed, there was obtained 11.0 g.

Analysis.-Calculated for C H NOS N=6.00%.

Found: N=5.85%.

Example XII (R-2333).-When the general procedure of Example II was repeated except that 11.3 g. (0.10 mol) of N-methallyl-n-propylamine, 10.1 g. (0.10 mol) of triethylamine, 10 g. (0.17 mol) of carbonyl sulfide, 9.7 g.

(0.10 mol) of chlorodimethyl sulfide and 150 cc. of petroleum ether solvent were employed, there was obtained 9.1 g. (38.9% yield) of methylmercaptomethyl N-methallyl-N-n-propylthiolcarbamate, B.P. (4.5 mm.) 144.0- 144.5 C., 11 1.5239.

Analysis.--Caloulated for C H NOS N=6.00%. Found: N=5.95%.

Example XIII (R-2336).When the general procedure of Example II was repeated except that 9.9 g. (0.10 mol) of N-methallylethylamine, 10.1 g. (0.10 mol) of triethylamine, 10 g. (0.17 mol) ofcarbonyl sulfide, 9.7 g. (0.10

mol) of chlorodimethyl sulfideand 150 cc. of petroleum ether solvent were employed, there was obtained 9.7 g. (44.4% yield) of methylmercaptomethyl N-methallyl-N- ethylthiolcarbamate, B.P. (4.5 mm.) 136l37 C., 1.5298.

Analysis.---Calculated for C H NOS N=6.40%. Found: N=6.2 3%,

messes Exam le XIV (R-2337). The general procedure of Example II was repeated except that 11.1 g. (0.10 mol) of N-m'ethallylallylamine, 10.1 (0.10 mol) of triethylamine, g. (0.17 mol) of carbonyl sulfide, 9.7 g. (0.10 mol) of chlorodimethyl sulfide and 150 cc. of tert. butyl alcohol solvent were employed. After completion of the reaction, 125 cc. of Solvent was distilled, the residual slurry was cooled to room temperature, diluted with 200 cc. of petroleum ether, B.P. 30-60" C. and the mixture was then worked up in the same manner as Example 11. There was obtained 17.2 g. (74.5% yield) of methylr'riercaptomethyl N-m'ethallyl N a llylthiol'carban'ia te, B.P. (4.5 mm.) 144.5145.5 C., a 1.5353.

AnalysisF-Calculated fol CIOHHNOSZI Found: N=5.84%.

Example XV (R-2338).--When the general procedure of Example XIV was repeated except that 13.4 g. (0.10 mol) of N-Z-chloroallyl-n-propylamine, 10.1 g. (0.10 mol) of triethylamine, 12.5 g. (0.21 mol) of carbonyl sulfide, 9.7 g. (0.10 mol) of chlorodimethyl sulfide and 150 cc. of tert. butyl alcohol were employed, there was obtained 18.4 g. (72.5% yield) of methylmeroaptomethyl N-Z- chloroallyl-N-n-propylthiolcarbarnate, B.P. (4.5 mm.) 1585-1605 C., n 1.5383.

Analysis.Calculated for C H NOS Cl: N=5.51%. Found: N=5.46%.

Example X VI (R-2339).-When the general procedure of Example XIV was repeated except that 13.2 g. (0.10 mol) of N-2-chloroallylallylamino, 10.1 g. (0.10 mol) of triethylamine, 10 g. (0.10 mol) of carbonyl sulfide, 9.7 g. (0.10 mol) of chlorodimethyl sulfide and 150 cc. of tert. butyl alcohol were employed, there was obtained 17.3 g. (68.5% yield) of methylmercaptomethyl N-Z-chloroallyl-N-allylthiolcarbamate, B.P. (4.5 mm.) 159-160 C., 11 1.5503.

Analysis-Calculated for C H NOS CI: N=5.55%. Found: N=5.38%.

Example XVII (R-2340).-When the general procedure of Example XIV was repeated except that 12.9 g. (0.10 mol) of di-n-butyl'amine, 10.1 g. (0.10 mol) of tr'iethylam'ine. 10 g. (0.17 mol) of carbonyl sulfide, 9.7 g. (0.10 mol) of chlorodimethyl sulfide and- 150 cc. of text. butyl alcohol were employed, there was" obtained 17.8 g. (71.3% yield) of methylmercapto'methyl N,N-di-n-butylthiolcarbamate, B.P. (4.5 mm.) 157.5-1-58.5 C., n 1.5078.

Analysis.Calculated for C H NOS N=5.61%. Found: N=5.41-%.

Example XVIII (R-2341).--When the general procedure of Example XIV was repeated except that 25.8 g. (0.20 mol) of di-isobut'ylamine, 20.2 g. (0.20 mol) of triethylamine, 17 g. (0.28 mol) of carbonyl sulfide, 19.3 g. (0.20 mol) of chlorodimethyl sulfide and 150 cc. of tert. butyl alcohol were employed, there was obtained 38.9 g. (78.1% yield) of methylmercaptomethyl, N,N di-isobutylthiolcarbamnte, B.P. (4.5 mm.) 143-145" C., 11 1.5059.

Analysis.Ca1culatcd for C H NOS N=5.61%. Found: N=5.54%.

Example XIX (R2342).When the general procedure of Example X-IV was repeated except that 13.4 g. (0.10 mol) of N-3-chloroallyl-n-propylamine, 10.1 g. (0.10 mol) of tn'ethylamine, 10g. (0.17 mol) of carbonyl sulfide, 9.7 g.- (0.10 mol) of chlorodimethyl sulfide and 150 cc. of tert. butyl alcohol wereemployed, there was obtained 1417 g; (57.8% yield) of meth'yl'mercaptomethyl N- 3 chloroallyl N n-propylthiolcarbamate, B.P. (4.5 mm.) 166.2-169 C., n 1.5432.

Analysis-Calculated for C HQ NOS CI: N=5.51%. Found: N='5.35%.

Exmnple XX (R-2343).-'-Whefi the general preeeau ra of Example XIV was repeated exam that 13.2 91 (0.1a mol) of N-3-chloroallylallylamine, 10.1 g. (0.10if1o1)1'of triethylamine, 10 g. (0.17 mol) of carbonyl sulfide, 9.7 g. (0.10 mol) of chlorodimethyl sulfide and 150. cc. of tort. butyl alcohol were employed, there was obtained 13.0 g. (51.5% yield) of methylmercaptomethyl N-3-chlordallyl- N-allylthiolcarbamate, B.P. (4.5 min.) 166-169 C.,

Analysis-Calculated for C H NOS C1: N=5.56%. Found: N=5.33%.

Example XXI (R-2344).--When the eneral recedure of Example XIV was repeated except that 12.0 g. (0.10 mol) of N-3-chloroallylethylamine, 10.1'g. (0.10

mol) of trietliylar'nine, 10 g. (0.17 mol) of carbonyl 5111-.

fide, 9.7 g. (0.10 11101) Of chlorddimethyl sulfide and cc. of tert. butyl alcohol were employed, there was obtained 14.7 g. (61.1% yield) of methylme'rcaptornetliyl N-3-chloroallyl-N-ethylthiolcarbamate, B.P. (4.5 mm.) 164.8-168" C., 11 1.5505. p

Analysis.-Calculated for C H NOS Cl: N=5.8 4%. Found: N=5.82%.

Example XXII (R-2 345).-When the general procedure of Example XIV was repeated except that 17.0 g. (0.20 mol) of piperidine, 20.2 g. (0.20 mol) of triethylamine, 16 g. (0.27 mol) of carbonyl sulfide, 19.3 g'. (0.20 mol) of chlorodimethyl sulfide and cc. of tort. butyl alcohol were employed, there wasobtained 27.3 g. (66.5% yield) of methylmercaptomethyl l-piperidi'ne carbothiolate, B.P. 4.5 mm.) 1525-15315 0., a3, 1.5578. 7

Analysis."Calculated for c,H ,Nos,; N+6.s1%'. Found: N=7.04%.

Example XXIII (R 2346).When the general procedure of Example XIV was repeated except that 19.8 g.

(0.20 mol) of Z-methylpip'eridine, 20.2 g. (0.20 mol) of I triethylamine, 16 g. (0.27 mol) oi -carbonyl sulfide, 19.3 g. (0.20 mol) of chlorodimethyl sulfide and 150 cc. of tert. butyl alcohol were employed, there was obtained 24.8 g. (56.6% yield) of methylmercaptomethyl 1-(2-methy1) piperidinecarbothiolate, B.P. (4.5 mm.) 155.5156.5 C., 11 3 1.5515.

Analysis.Calculated for c,H, Nos,= N 6.37 Found: N"=6.59%.

7 Example XXIV (R 2347).-When the general procedure of Example XIV was repeated except that 14.2 g. (0.20 mol) of pyrrolidine, 20.2 g. (0.20 mol) of triethyl amine, 17 g. (0.28 mol) of carbonyl sulfide, 19.3 g. (0.20 mol) of chlorodimethyl sulfide and 150 cc. of tert. butyl alcohol were employed, there was obtained 25.4 g.

(66 .3% yield) of methylmercaptomethyl l-pyrrolidine carbothiolate, B.P. 4.5 mm.) 1535-1540" (2., 1155 1.56.19.

Analysis.-Calculated for C7H13NOS21 N'=7.31%". Found: N=7.42%.

Example XXV (R28I6).When the general proce-' dure of ExampleXIV was repeated except max 2015 g'}. (0.28 mol) diethylamine, 28 .3 g. (0.2811101) of-'tri' ethylamine,-22.8 g. (0.38 mol of carbonyl sulfide, 311.8 g.

(0.28 mol) of chloromethyl ethyl sulfide arid 200 cc. of

(0.20 mol) of di-n-propylamine, 20.2 g. (0.20mo1) of 7 triethylamine, 16 g. (0.27 mol) of carbonyl sulfide, 22.1 g. (0.20 mol) of chloromethyl ethyl sulfide and 150 cc. of tert. butyl alcohol were employed, there was obtained 32.6 g. (69.4% yield) of ethylmercaptomethyl N,N-di-npropylthiolcarbamate, B.P. (10 mm.) 163.5-164.0 C., 11 1.5105.

Analysis.Calculated for C I-I NOS N=5.95%.

Found: N=5.76%. Example XX VII (R2823).When the general procedure of Example XIV was repeated except that 20.2 g. (0.20 mol) of N-ethyl-n-butylamine, 20.2 g. (0.20 mol) of triethylamine, 16 g. (0.27 mol) of carbonyl sulfide, 22.1 g. (0.20 mol) of chloromethyl ethyl sulfide and 150 cc. of tert. butyl alcohol were employed, there was obtained 33.1 g. (70.4% yield) of ethylmercaptomethyl N-ethyl-N-n-butylthiolcarbamate, B.P. (10 mm.) 164.5- l 66.0 C., n 1.5104.

Analysis.Calculated for C H NOS N=5.95%. Found: N=5.85%.

Example XX VIII (R-2824).-When the general procedure of Example XIV was repeated except that 19.4 g. (0.20 mol) of diallylamine, 20.2 g. (0.20 mol) of triethylamine, 16 g. (0.27 mol) of carbonyl sulfide, 22.1 g. (0.20 mol) of chloromethyl ethyl sulfide and 150 cc. of tert. butyl alcohol were employed, there was obtained 29.8 g. (64.5% yield) of ethylmercaptomethyl N,N-diallylthiolcarbamate, B.P. (10 mm.) 164.0-164.1 C., ri 1.5330.

Analysis.--Calculated for C H NOS N=6.05%. Found: N=6.04%.

Example XXIX (R-2826).When the general pro cedure of Example XIV was repeated except that 9.9 g. (0.10 mol) of N-allyl-n-propylamine, 10.1 g. (0.10 mol) of triethylamine, 10 g. (0.17 mol) of carbonyl sulfide, 11.1 g. (0.10 mol) of chloromethyl ethyl sulfide and 150cc. of tert. butyl alcohol were employed, there was obtained 16.0 g. (68.6% yield) of ethylmercaptomethyl N-allyl-N-n-propylthiolcarbamate, B.P. (10 mm.) 162.5- 163.0 C., 11 1.5216.

Analysis.Calculated for C I-I NOS N=6.00%. Found: N=5.83%.

Example XXX (R-2829).-When the general procedure of Example XIV was repeated except that 9.9 g. (0.10 mol) of N-methallylethylamine, 10.1 g. (0.10 mol) of triethylamine, 10 g. (0.17 mol) of carbonyl sulfiide, 11.1 g. (0.10 mol) of chloromethyl ethyl sulfide and 150 cc. of tert. butyl alcohol were employed, there was obtained 16.0 g. (68.6% yield) of ethylmercaptomethyl N-methallyl-N-ethylthiolcarbamate, B.P. (10 mm.) 160.0-160.5 C., 11 1.5231.

Analysis.Calculated for C H NOS N=6.00%. Found: N=5.89%.

Example XXXI (R-2832).When the general procedure of Example XIV was repeated except that 11.1 g. (0.10 mol) of N-methallyl-allyl amine, 10.1 g. (0.10mol) of triethylamine, 10 g. (0.17 mol) of carbonyl sulfide, 11.1 g. (0.10 mol) of chloromethyl ethyl sulfide and 150 cc. of tert. butyl alcohol were employed, there was obtained 16.5 g. (67.4% yield) of ethylmercaptomethyl N-methallyl-N-allylthiolcarbamate, B.P. 10 mm.) 166.5-167.0 C., n 1.5285.

Analysis.-Calculated for C H NOS N=5.7l%. Found: N=5.51%.

Example XXXII (R-2837).When the general procedure of Example XIV was repeated except that 12.0 g. (0.10 mol) of N-3-chloroallylethylamine, 10.1 g. (0.10 mol) of triethylamine, 10 g. (0.17 mol) of carbonyl sulfide, 11.1 g. (0.10 mol) of chloromethyl ethyl sulfide and 150 cc. of tert. butyl alcohol were employed, there was obtained as a residue 20.4 g. (80.4% yield) of ethylbromoethyl methyl sulfide was rapidly added.

mercaptomethyl N-3-chloroa1lyl-N-ethylthiolearbamate, n 1.5416.

Analysis.-Calculated for C H CINOS N=5.52%; Cl=13.97%. Found: N=5.35%; Cl=13.70%.

Example XXXIII (R-2838).-When the general procedure of Example XIV was repeated except that 8.7 g. (0.10 mol) of N-methyl-n-butylamine, 10.1 g. (0.10 mol) of triethylamine, 10 g. (0.17 mol) of carbonyl sulfide, 11.1 g. (0.10 mol) of chloromethyl ethyl sulfide and 150 cc. of tert. butyl alcohol were employed, there was obtained 14.8 g. (66.9% yield) of ethylmercaptomethyl N- methyl-N-n-butylthiolcarbamate, B.P. (10 mm.) 161.5 162.0 C., 11 1.5155.

Analysis-Calculated for C H NOS Found: N=6.20%.

Example XXXIV (R-2843).-When the general procedure of Example XIV was repeated except that 9.9 g. (0.10 mol) of 2-methylpiperidine, 10.1 g. (0.10 mol) of triethylamine, 10 g. (0.17 mol) of carbonyl sulfide, 11.1 g. (0.10 mol) of chloromethyl ethyl sulfide and 150 cc. of tert. butyl alcohol were employed, there was obtained as a residue 15.4 g. (66.1% yield) of ethylmercaptomethyl 1-(Z-methyl)piperidinecarbothiolate, 11 1.5450.

Analysis.Calculated for C H NOS N=6.00%. Found: N=6.31%.

Example XXXV (R2844).-When the general procedure of Example XIV was repeated except that 12.7 g. (0.10 mol) of N-ethylcyclohexylamine, 10.1 g. (0.10 mol) of triethylamine, 10 g. (0.17 mol) of carbonyl sulfide, 11.1 g. (0.10 mol) of chloromethyl ethyl sulfide and 150 cc. of tert. butyl alcohol were employed, there was obtained as a residue 20.1 g. (77.0% yield) of ethylmercaptomethyl N ethyl-N-cyclohexylthiolcarbamate, 11 1.5259.

Analysis.-Calculated for C H NOS N=5.36%. Found: N=4.89%.

Example XXXVI (R-2850).-The general procedure of Example XIV was repeated except that 5.0 g. (0.068 mol) of diethylamine, 6.8 g. (0.068 mol) of triethylamine, 6.9 g. (0.115 mol) of carbonyl sulfide and 125 cc. of tert. butyl alcohol were used. The reaction mixture was then heated to 50 C. and 11.5 g. (0.074 mol) of 2- After several minutes, triethylammonium bromide began to precipitate from the solution. The reaction mixture was kept at 50 C. for 20 hours, cc. of solvent was distilled and the reaction mixture was then worked up in the usual manner. There was obtained 14.1 g. (55.3% yield) of 2 methylmercaptoethyl N,N-diethylthiolcarbamate, B.P. (10 mm.) 149.5-150.0 C., n 1.5219.

Analysis.Calculated for C l-1 N08 N=6.76%. Found: N=6.72%.

Example XXX VII (R-2854).-When the general procedure of Example XXXVI was employed except that 6.8 g. (0.068 mol) of N-ethyl-n-butylamine, 6.8 g. (0.068 mol) of triethylamine, 6.9 g. (0.115 mol) of carbonyl sulfide, 11.5 g. (0.074 mol) of 2-bromoethyl methyl sulfide and cc. of tert. butyl alcohol were employed, there was obtained 10.4 g. (65.0% yield) of 2-methylmercaptoethyl N ethyl-N-n-butylthiolcarbamate, B.P. (10 mm.) 1680-1690 C., 71 1.5126.

Analysis.-Calculated for CmHmNOSaI Found: N=5.91%.

Example XXX VIII (R-2855).When the general procedure of Example XXXVI was employed except that 7.2 g. (0.074 mol) of diallylamine, 7.5 g. (0.074 mol) of triethylamine, 6.9 g. (0.115 mol) of carbonyl sulfide, 11.5 g. (0.074 mol) of Z-bromoethyl methyl sulfide and 125 cc. of tert. butyl alcohol were employed, there was obtained 11.4 g. (72.6% yield) of Z-methylmercapto 15s.s ethyl N,N dizglylthiolcarbamate, B P (10 mm) Oats Cucumbers Radish 169.0 0., 1.5353. I compound Analysis.Calculated for CIOHI'INOSQ: N=6.05%. v Germ Growth Germ Growth Germ Growth Found: N=6.09%. 6 Example XXXIX (R-2857).Wl1en the general pro- 0 0 cedure of Example XXXVI was employed except that 8 g i 6.7 g. (0.07 mol) of N-allyl-n-propylamine, 6.8 g. (0.07 0 25 3 75 4 mol) of triethylamine, 6.9 g. (0.12 mol) of carbonyl 5111- 8 8 g g fide, 10.5 g. (0.07 mol) of 2-bromoethyl methyl sulfide 10 0 25 3 75 s and 125 cc. of tort. butyl alcohol were employed, there 8 8 was obtained 9.4 g. (59.5% yield) of Z-rnethylmercaptog 8 g eflhyl N-allyl-N-n-propylthiolcarbamate, B.P. 10 mm.) 0 50 2 1555-1575" c., 1.5238. a I 15 3 f3 3 f Analysis.-Cal culated for C H NOS N=6.00%- 8 8 g Found: N=6.08%. v 0 0 0 The compounds of the present invention have been 8 g 23 tested as herbicides and found very efiective as the fol- 5 15 5 lowing typical tests show. Some of the compounds are g g quite selective in their action and can be used to eradi- 8 8 8 cate or control one type of plant, while another type of 0 0 0 plant is relatively unatfected. g g g3 In making the following tests, seeds were planted in 0 0 25 3" pots and shortly thereafter the compound under test 25 8 g was applied to the pots as a drench at the rate of 365 g g 72 pounds per acre. The pots were placed in a ,g'reenhouse 0 0 5 and watered at suitable intervals and the germination 8 and growth of the seeds was compared with similarly g g 5 planted seeds to which no herbicide was added. In each 0 0 11:11:: 15 1 case, germination was reported on the scale 0-100%, 0 Q 25 2 while growflh was l 17 f based on The above tests were then repeated using application h s s Whlch m T 5 mdlcates rates of 10 and 40 pounds per acre with the following trialv germination and normal growth. results:

Peas Corn Radish Rye Cucumber Compound LRsJ I Ge. Gr Ge. Gr. Ge. Gr. Ge Gr. Ge. Gr.

. 10 100 a 190 10 100 10 0 5 R4264 1 4 100 10 0 10 $2265 10 100 1 100 5 100 10 0 5 40 100. 1 150. 10 100 10 0 10 R2340 10 100 10 100 10 100 10 100 10 40 100 10 190 9 100 10 50 s R4341 10 100 5 19 100 19 100 19 40 100 5 105 10 105 10 25 4. 1mm 10 100 s 100 9 100 10 5 1o 49 109 4 190 5 109 10 0 4 R4267. 10 100 5 100 10 190 10 0 10 49 100 3 75 4 100 10 0 1 H4296 10 100 9 199 10 109 10 o 10 40 50 4 100 10 100 10 0 10 R4323 10 100 4 109 10 100 10 0 s i8 i88 2 $8 13 l88 l8 8 2 40 100 1 100 6 100 10 o 4 $2326. 7 19 .109 4 100 10 100 10 o 7 49' 100 1 100 10 100 10 o a R4328 10 100 4. 100' 10 100 10 0 1o 40, 75 a 100 10 100 10 o 4 R4329 10- 100 5 100 19 100 10 25 10 4 40 100 t 4 100 9 100' 7 o 3- 114330 10 100 5 100 10 100 10 50 10 40 100 a 100 10 109 s o 3 E2333 10 100 4 190 10 100 10 100 s 40 100 2 109 s 100 7 50 2 R 2336 10 100 a 100 19 100 10 100 5 40 75 1 190 10 100 10 100 10 1mm 10 100 5 100 10 100 10 100 10 40 100 a 100 10 100 10 75 5 R4338 10 100 5 100 10 100 10 10 40 100 5 100 10 100 10 100 8 E2339 10 100 7 100 10 100 10 100 10 40 100 4 100 s 100 10 5o 7 1H3 10 100 10 100 10 100 10 100 10 40 100 5 100 10 100 10 100 6 K2343 10 100 10 10 100 10 100 10 40 100 4 100 s 109 10 50 4 1H3 19 100 s 100 10 100 10 100 10 4o 50 2 100 5 75 5 50 a R4345 10 100 5 100 10 100 10 100 9 40 100 a 100 4 100 5 100 4 10 100 2 100 9 100 10 100 7 4o 25 0+ 100 4 100 5 15 0+ 10 100 8 100 8 100 10 100 5 40 75 2 100 2 100 5 50 a 10 100 7 100 10 100 10 100 7 40 100 a 100 9 100 s 75 5 19 100 5 199 10 100 9 100 10 40 100 1 100 8 100 s 30 3 Peas Corn Radish Rye Cucumber Compound LRsJ Ge Gr Ge Gr. Ge Gr Ge Gr, Ge. Gr.

10 100 9 100 10 100 10 50 5 100 10 R4823 i 40 100 3 100 7 100 6 100 a R4824 10 100 9 100 10 100 10 100 3 100 B 40 100 3 100 8 100 7 0 0 R 2826 10 100 7 100 10 100 10 100 0+ 100 9 10 100 3 100 8 100 0 0 R4829 100 4 100 9 100 9 100 1 100 a 40 100 2 100 7 100 7 75 0+ 0 R4832 10 70 6 100 10 100 9 100 0+ 100 7 40 100 2 100 9 100 7 0+ 0 R4837 10 100 0 100 7 100 10 100 3 100 10 40 100 6 100 10 100 8 80 0+ 100 9 E4838 10 100 8 100 9 100 10 100 0+ 100 9 40 100 4 100 7 100 7 70 0+ 100 6 40 100 1 100 7 100 10 80 0+ 100 4 R4844 10 100 8 100 10 100 10 100 1 100 10 40 100 7 100 9 100 10 100 0+ 100 4 8 R 285O 10 100 5 100 10 100 10 50 0+ 100 9 40 100 1 100 7 100 6 10 0+ 100 6 R4854 10 100 7 100 10 100 10 100 0+ 100 10 40 100 3 100 5 100 6 0 100 3 R 2855 10 100 3 100 8 100 10 100 0+ 100 1D 40 100 l 100 8 100 6 20 0+ 100 4 R4857 10 100 2 100 10 100 10 100 0+ 100 10 40 100 1 100 7 100 6 0 i..-- 35 l The compounds of the present invention may be used as preemergence or postemergence herbicides and may be applied in a variety of ways at various concentrations. They may be combined with suitable carriers and applied as dusts, sprays or drenches. The amount applied will depend on the nature of the seeds or plants to be controlled and the rate of application may vary from 1 to 500 pounds per acre. One particularly advantageous way of applying the compounds is as a narrow band along a row crop, straddling the row.

We claim:

1. The method of combating weeds comprising: applying to the soil a phytotoxic amount of a compound having the formula RISRIS-C-N wherein R is a lower alkyl radical, R is selected from the group consisting of a methylene radical and a. lower polymethylene radical, and wherein R and R are selected from the group consisting of one (1) lower alkyl, cyclohexyl, lower alkenyl and lower haloalkenyl radicals: (2) a single tetramethylene group bonded through each of its terminal carbon atoms to the nitrogen atom of the thiolcarbamate; and (3) a single pentamethylene group, said pentamethylene group being selected from the group consisting of methyl substituted and unsubstituted pentamethylene bonded through each of its terminal carbon atoms to the nitrogen atom of the thiolcarbamate.

2. The process of claim 1 wherein the compound is applied in a narrow band to a row crop at a rate of application from about one-half to about twenty pounds per acre of area actually treated.

3. The method of combating weeds comprising: applying to the soil a phytotoxic amount of methylmercaptomethyl N,N-diethylthiolcarbamate.

4. The method of combating weeds comprising: applying to the soil a phytotoxic amount of methylmercaptomethyl N,N-di-n-propylthiolcarbamate.

5. The method of combating weeds comprising: applying to the soil a phytotoxic amount of methylmercaptomethyl N-allyl-N-ethylthiolcarbarnate.

6. The method of combating weeds comprising: applying to the soil a phytotoxic amount of methylmercaptomethyl N-methallyl-N-ethylthiolcarbamate.

7. The method of combating weeds comprising: applying to the soil a phytotoxic amount of methylmercaptomethyl 1-(2-methyl)-piperidinecarbothiolate.

References Cited in the file of this patent UNITED STATES PATENTS 2,197,574 Watt Apr. 16, 1940 2,396,789 Hunt Mar. 19, 1946 2,562,011 Baumgartner July 24, 1951 2,642,451 Weiyland Jan. 16, 1953 2,687,348 Kosmin Aug. 24, 1954 2,690,440 Himel Sept. 28, 1954 2,842,554 Sullivan July 8, 1958 2,883,318 Bras Apr. 21, 1959 FOREIGN PATENTS 205,460 Australia Mar. 8, 1956 

1. THE METHOD OF COMBATING WEEDS COMPRISING: APPLYING TO THE SOIL A PHYTOTOXIC AMOUNT OF A COMPOUND HAVING THE FORMULA 